Well‐Defined Iron Complexes as Efficient Catalysts for “Green” Atom‐Transfer Radical Polymerization of Styrene,Methyl Methacrylate,and Butyl Acrylate with Low Catalyst Loadings and Catalyst Recycling

Environmentally friendly iron(II) catalysts for atom‐transfer radical polymerization (ATRP) were synthesized by careful selection of the nitrogen substituents of N,N,N‐trialkylated‐1,4,9‐triazacyclononane (R₃TACN) ligands. Two types of structures were confirmed by crystallography: “[(R₃TACN)FeX₂]” complexes with relatively small R groups have ionic and dinuclear structures including a [(R₃TACN)Fe(μ‐X)₃Fe(R₃TACN)]⁺ moiety, whereas those with more bulky R groups are neutral and mononuclear. The twelve [(R₃TACN)FeX₂]_n complexes that were synthesized were subjected to bulk ATRP of styrene, methyl methacrylate (MMA), and butyl acrylate (BA). Among the iron complexes examined, [{(cyclopentyl)₃TACN}FeBr₂] ( 4 b ) was the best catalyst for the well‐controlled ATRP of all three monomers. This species allowed easy catalyst separation and recycling, a lowering of the catalyst concentration needed for the reaction, and the absence of additional reducing reagents. The lowest catalyst loading was accomplished in the ATRP of MMA with 4 b (59 ppm of Fe based on the charged monomer). Catalyst recycling in ATRP with low catalyst loadings was also successful. The ATRP of styrene with 4 b (117 ppm Fe atom) was followed by precipitation from methanol to give polystyrene that contained residual iron below the calculated detection limit (0.28 ppm). Mechanisms that involve equilibria between the multinuclear and mononuclear species were also examined.     

基于CSP工艺铽对Q345B再结晶的影响

以CSP工艺生产的Q345热轧钢板为研究对象,采用Gleeble-1500D热模拟实验机进行单、双道次轧制模拟实验,研究了稀土铽(Tb)对Q345B钢再结晶行为的影响.结果表明,稀土铽(Tb)能够明显地推迟Q345B钢的动态再结晶,使对应峰值应力在低温轧制时提高约10%,而对980℃以上时的峰值应力影响不明显;980℃以上轧制时,稀土铽(Tb)能够明显的降低间隔时间1.5 s时的静态软化率,但随间隔时间的增加,稀土铽(Tb)对静态软化率的影响减弱;加入稀土铽能够提高完全再结晶区温度,扩大部分再结晶区.     

Synthesis and structures of two novel indolo[3,2-b] carbazole derivatives

Indolocarbazole derivatives have already been reported to be good organic semiconductor candidates. The knowledge of the relationship between the structure and packing of molecules in crystal is indispensable in design of high performance organic semiconductor materials. Two new indolocarbazole derivatives, 2,8-dibromo-5,11-di-[4-(isoindole-1,3-dione-2-yl)butyl]indolo[3,2-b]carbazole (I) and 2,8,6,12-tetrabromo-5,11-di-(4-chlorobutyl)indolo[3,2-b]carbazole (II) have been synthesized and the crystal structures have been studied. The dichloromethane solvate of (I), C₄₂H₃₂Br₂N₄O₄ · 2CH₂Cl₂, is monoclinic, space groups P2₁/n. Unit cell parameters are a = 11.6847(2), b = 12.6942(2), c = 13.7899(2) Å, β = 91.8220(10)°. Unlike other indolo[3,2-b]carbazole derivatives, there is no any π–π stacking between the indolocarbazole backbone of two adjacent molecules in the crystal. Since the isoindole-1,3-dione-2-yl is introduced in 5- and 11-positions in the molecule, the intermolecular short contacts mainly localize in between the pendant groups of the neighboring indolocarbazole molecules. The compound (II) is also monoclinic with P2₁/c space groups. Unit cell parameters are a = 4.6427(9), b = 11.425(2), c = 24.511(4) Å, β = 93.47(1)°. In contrast with compound (I), the molecules of (II) possess strong face-to-face π–π stacking. The crystal structures were studied in detail. It is concluded that linear pedant groups benefit to co-facial π–π interaction. Additionally, the molecule electronic spectra were studied by quantum chemistry theoretical calculation.     

343 nm飞秒激光制备微孔阵列以增强聚氨酯合成革透湿性

为了提高聚氨酯(PU)合成革透湿性,分别使用343 nm飞秒激光和作为对比的1030 nm飞秒激光及1064 nm纳秒激光制备微孔阵列。采用扫描电镜(SEM)和3D激光扫描显微镜对比研究了微孔形貌。结果表明,343 nm飞秒激光可以制备出效果最佳的微孔。此外,分析了3种激光与PU涂层的作用机理,揭示了343 nm飞秒激光合成革微钻孔过程仅表现为光化学烧蚀,光化学和光热烧蚀同时发生于1030 nm飞秒激光钻孔过程,而1064 nm纳秒激光只显示了光热烧蚀。激光合成革表面钻孔后,测量其透湿性和抗张力。结果显示: 微孔密度越大,皮革透湿性(WVP)越大而抗张力越低,脉冲重叠的增加会导致WVP的增加和抗张力的下降;同时,随着脉冲重叠从91.7%降到50%,微孔直径从45 μm降低到30 μm,而微孔锥度从0.7°增加到12.1°;当脉冲重叠率为91.7%,微孔密度为2550/cm²时,最大的WVP增长率为306%。     

非化学配比锰基钙钛矿输运特性研究

本文报道了用溶胶凝胶法并经过低温(900℃)后处理制备的具有非化学配比的La2/3Ca1/3Mn1-xO3(x=0～0.10)多晶样品的电输运和磁性质的实验研究.结果表明,随x的增加,样品呈现出明显增强的非本征磁电阻效应,同时其本征磁电阻效应减弱.实验还观察到样品的颗粒尺寸随x的增加而减小的现象.基于样品的结构特征,本文讨论了其独特输运性能的形成原因.     

线型离子阱中空间电荷效应的理论分析

线型离子阱中的离子在射频场作用下做宏观的久期运动,久期运动频率与实验参数有关.但当离子阱中囚禁大量同种电荷的离子时,空间电荷效应会导致离子间存在相互排斥的库仑力,使离子的运动频率发生漂移.本文通过求解泊松方程计算了空间电荷产生的附加电场的解析表达式,在小振动近似下理论计算了该附加电场对久期运动频率的影响,模拟了不同离子云中心密度下久期频率的漂移,讨论了离子云的数目、温度与实验参数之间的关系.对用离子阱进行的频标实验、碰撞实验和其他方面的研究都具有重要的指导意义.     

Spectral boundary controllability of networks of strings

In this Note we give a necessary and sufficient condition for the spectral controllability from one simple node of a general network of strings that undergoes transversal vibrations in a sufficiently large time. This condition asserts that no eigenfunction vanishes identically on the string that contains the controlled node. The proof combines the Beurling–Malliavin's theorem and an asymptotic formula for the eigenvalues of the network. The optimal control time may be characterized as twice the sum of the lengths of all the strings of the network. To cite this article: R. Dáger, E. Zuazua, C. R. Acad. Sci. Paris, Ser. I 334 (2002) 545–550.     

Research on the ultrafast fluorescence property of thylakoid membranes of the wild-type and mutant rice

A high yielding rice variety mutant (Oryza sativa L., Zhenhui 249) with low chlorophyll b (Chl b) has been discovered in natural fields. It has a quality character controlled by a pair of recessive genes (nuclear gene). The partial loss of Chl b in content affects the efficiency of light harvest in a light harvest complex (LHC), thus producing the difference of the exciting energy transfer and the efficiency of photochemistry conversion between the mutant and wild-type rice in photosynthetic unit. The efficiency of utilizing light energy is higher in the mutant than that in the wild-type rice relatively. For further discussion of the above-mentioned difference and learning about the mechanism of the increase in the photochemical efficiency of the mutant, the pico-second resolution fluorescence spectrum measurement with delay-frame-scanning single photon counting technique is adopted. Thylakoid membranes of the mutant and the wild-type rice are excited by an Ar^+ laser with a pulse width of 120 ps, repetition rate of 4 MHz and wavelength of 514 nm. Compared with the time and spectrum property of exciting fluorescence, conclusions of those ultrafast dynamic experiments are: 1) The speeds of the exciting energy transferred in photo-system I are faster than that in photo-system II in both samples. 2) The speeds of the exciting energy transfer of mutant sample are faster than those of the wild-type. This might be one of the major reasons why the efficiency of photosynthesis is higher in mutant than that in the wild-type rice.     

Three-step iterative methods with eighth-order convergence for solving nonlinear equations

A family of eighth-order iterative methods for the solution of nonlinear equations is presented. The new family of eighth-order methods is based on King’s fourth-order methods and the family of sixth-order iteration methods developed by Chun et al. Per iteration the new methods require three evaluations of the function and one evaluation of its first derivative. Therefore this family of methods has the efficiency index which equals 1.682. Kung and Traub conjectured that a multipoint iteration without memory based on n$n$ evaluations could achieve optimal convergence order 2ⁿ⁻¹$2^{n-1}$. Thus we provide a new example which agrees with the conjecture of Kung–Traub for n=4$n=4$. Numerical comparisons are made to show the performance of the presented methods.     

被动谐波锁模Er3+/Yb3+共掺双包层光纤环形腔激光器

为了实现高重复频率和高功率的光脉冲,实验采用Er3+/Yb3+共掺双包层光纤作为增益介质,稳定的中心波长为976 nm的高功率半导体激光器作为泵浦源,利用非线性偏振旋转锁模技术,得到稳定的自起振锁模光脉冲。当泵浦功率为2.4 W时,激光器输出重复频率为8.829 MHz的连续锁模光脉冲,平均输出功率为52.5 mW,自起振锁模泵浦阈值功率为0.6 W,并观测到了稳定的高阶谐波锁模、调Q和调Q-锁模光脉冲输出。